Feed supplement



Patented July 15, 1952 FEED SUPPLEMENTl Hugh a. Stiles,-St. Mary-of-theQWoods, Ind., as-

signor .to Commercial Solvents Corporation, Terre Haute,I'n d., a corporation of Maryland No, Drawing. Application] anuary 20, 1951,

Serial No.- 207,065

I f9Claims.

The present. invention relates to a new and improved livestock-feed supplement derived from sugar containing materials: More particularly, it relates to a feed supplement for ruminants derived ,from ammonia and sugar-containing materials such as molasses and the like. Shortages of the most desirable forms of natu-v rally occurring feedstuffs have made it necessary from time to time to use various substitutes deficient in oneor more of the elements essential i na balanced ration. 7 It has been the custom for some time, therefore, to formulate feedstufis using-varying quantities of different materials so as. to give a mixturehaving the proportions of the various food constituentsdesirable for feeding purposes. This practice has several admaterials which would otherwise either go .to

, waste or else be inefliciently used and also it permits the formulation of fe'edstuifs designed for specific feeding purposes.

-Among the materials, which have been frequently usedon an extensive scale as mixed feed constituents are materials containing varying amounts of diiferent types of sugars, usually,

resulting as a, by-product from the manufacture of foodstuffs for human consumption, as for example, cane or blackstrap molasses, hydrol syrup, [and the. like. Another somewhat similar sugar- ]containingmaterial, used 'on a somewhat lesser sealejlisj the syrup obtained by the concentration of. the molasses mash from which fermentation I ethyl alcohol has. been removed by distillation.

This product is referred to" in the .trade as CDMS (condensed di'stillers molasses solubles) Sugar-containing syrups, such as cane molasses,'are'very palatable and are much'relished by livestock and when mixed with other materials induce the stock to eat roughage and less palat- Table materials with less waste of the latter than 'there would be otherwise. molasses may be worth fully as much or even more than corner other grain and'in-fact is one 1.of the cheapest sources of carbohydratesfor the y feed manufacturer. In addition, sugar-containing materials such as cane molasses have a mild g j laxative-effect that is beneficial when the other Qfeeds in the ration are constipating.

When thus fed The most readily available sugar-containing materials suitable forlivestock feeding are probablycane or blackstrap molasses, inverted molas- -;ses, hydrol syrup, and CDMS.

Cane or blackstrap molasses of the usual grade contains 5% or more of sugars, which are the v Jfonly important" organic nutrients. 'It contains only approximately 2.8% nitrogen calculated as 1 protein, on the average, andhence when large amounts of molasses are fed it is especially important that sufiicient protein .be furnished by the rest of the ration in orderflto give a. satisfactorily .balanced mixed feed.

In the past, it has been customary when using molasses as a feed constituentto make up the 7 protein deficiencyby incorporating in the feed.

vantages "in that it provides a method of utilizing formly withv the feeds have occasionallycaused the death of animals which do not possess digesprotein deficiency by incorporating in the feed mixture expensive protein-containing materials such as .soybeanbil meal, cottonseed oil meal, g and the like- I Attempts have also been made to make up: the

other nitrogen-containing materials such as urea and ammonium salts. None of these or other suggested materials has been a completely satisfactory substitute for the desired proteins for a number of reasons. Ammonium salts and urea are utilized to a limited degree but are relatively toxic and since they are not readily mixed unitive systems permitting of emcient utilization of high concentrations of nitrogen inv such forms.

I have now discovered that ammonia may be readily and economically converted into a form which may be efiiciently utilized by ruminants by subjecting the ammonia to reaction with sugar- ,containing materials such as cane or blackstrap molasses, inverted molasses, wood sugar molasses,

' 'hydrol syrup, CDMS," citrus molasses (condensed citrus solubles) and the like. The product thus obtained retains many of the advantageous properties of the original sugar-containing materials with the added advantage that it is no longer deficient in nitrogen which can be efficiently utilized by livestock; By means of a.

relatively inexpensive ammonization step the sugar-containing materials are thus converted intovhighlysatisfactory feed supplements with which balanced mixed livestock feeds can be produced at a substantiallylower cost than with other previously available materials. 7

"My new nitrogen-containing feed supplement is prepared by v subjecting a sugar-containing liquid. having at least about 25% but not in excess of about solids therein, to reaction with ammonia in-either the aqueous, gaseous, or anhydrous liquid form. Whilev the reaction. can be carried out at room temperature long periods .of time are ordinarily required in order to give the .desired' degree of ammonization, This is particularly the case if the ammonia isused in dilute form, for example as aqueous ammonia i Y 535. p

out the reaction at as high temperature as possible 5 in order, to complete the ammoniation in the shortest 'eriod oftirrieg' However.be'causeof the dangef'o caramenzanbn of the" sugar and other reactions which take place in the complex sugar,-

been obtained and then heating the resulting solution at the desired temperature until fixation of the ammonia has been attained and then adding additional ammonia, if required, to give a final product of the desired degree of fixed nitrogen content. Or, preferred t e ammonia in tliedsiredifmm n :the pre- "viously heated "sugar contaifiing solution. Ob-

viously, the operation may be carried out either containing mixtures of commerce which are availi'dcontinuously or as a batch operation. If pres- "-s 1'Q" Iid suitable mixing equipment are available,

able at low enough prices to be used as ingredients of animal feeds, the maximum temperature utilizable in my process is somewnaebewwwhat at which most rapid ammoniatio 60 to 80 C. when the operation is carriedv on asa batch process. Under such condition heating for gives asatisfactory product, atu're is {employed "long reaction v a into" several weeks time'are'remired: 13y carryingout the reaction at tempera,- tufs'i of the order of v1"1 C, "satisfactory amfrioniation 'is' 'effe'ote fwithin the period er -'o ne 5" itiping the heated tube. The reaction'can then be regulated byyarying the diameter and length of the heated fs'etion car the reactor tubes and f the temperatakes fplafie. While the reaction may beefftedat"trhpefa=' 15 tures ranging from to 150? Gfinost satisfactoryG results are obtained at temperatures rangiilg fififilff 1 n is 'morefealsily regulated imixture' of reactants through a of the reactor'andthe rate of flow of therea" tants "therethroii'gh. Under such operating g5 j' lconditioiis temp ratur s up'to 'theorder m: 140" qfha've been found to "give satisfactory "results when heatingforipriods of timerangingfrom 5 .to "a pro nm'ately '15 "minutes, Heating ,Qto. approximately 130, 'C, for about 15' ininutes'im a very satisfactory product. Under "Such conditions it is -u"sually necessary to apply pres- 'n' s stem order to keep the how -era'nd rpreferjto use s v I 1 ne'des ryii'or'den tof'm'ain- ."tain the-liduid: hase. At trnperatures' oftho se described} substantialcarin j excessive darli'nifigflahd otli Y {sugar conta'iningf .i'so'lfi sy -begm" to take place, and a 2mm product deiuddlyless",desira1o'le' for use as a feed "incr ment results. f

The use of aqueous 'a'fnirioni'a jisffgrierally uniexcess if desirableib ecaiisefiof the exc ss ve dilutibnof the varying suitable quantities of anhydrous liquid ammonia nbe mixedwith 'the sugar-containing liquids instead of usiiigj aseous anhydrous ammonia.

"'Ihemd'd'itidn ofammonia to the sugar-contain- Lingv materialin slight excess of that to be fixed generally gives the best results. However, the presence of excessive amounts of free ammonia "'inthefinal product is undesirable in feed constituents. I have found that if I carry out the --ainmoniation so tlia't the -7 1 11 915 the prddiiot whih'womd be -'in -the-digestive"systm o obtainedsatisfactoryFproductsi by the use 0 acids. "such as hydrochloric; i'sulfu'ri'c, for phosphoric acids. I I

"The fouowmg'exampies' ilIustratetIieT reparation' of my fie'wf'd 5:11pplfe llien13. -,'It 1 101 1Id'be understood, however, h samples "are 'illustrative onlyalnd th an odlfdsatisfactory materials rram "other sugar-containing "inateri ails and I eanwary' the prddeduie' g'riiia lly V V vary ng arm-de ts 0r 2s-% a aeb us were added 0 1500" .grafiis'fof mackstr "m iasses in s -ri ck. rciundrpottom flasks fitted fwith mechanicalstirrers'aiidtli ointr s A'mmittdjftaprdce drow rymg per ods "of timea mirerent'tmperatures. "Table below shows "the, resultsobtairiediirfderitiise operatingeormitronsy f wouldjbe impractical'and excessively costly. Ammoniation" isjthr'e'fore preferably fi'e'cted by either passing-gaseous trans tions 2; mriiainto ithe :sugar containing solution bing'jam'moriiated until saturated or the desired concentration fias the concentration of '70 Anhydrous a monia ga WasQpQsSeiihi'qugh -.a spargerinto 500 .grams o f h-ydrolsyi updthe N c ry s'talliiatin' of diitrose and containing sodium. chloridefrom'. the neutralization of the acid) in varying amounts in 3 neck round-bottom flasks provided with mechanical stirrers and thermometers. Table II below shows the results of a series of expriments so conducted.

fritted' glass dispenser into 471.7 grams of wood sugar molasses in a beaker until a total of 28.3 grams of ammonia had been added. The molasses was then heated on a steam bath for approximately one hour, the pH of the wood molasses syrup at the beginning of the operation from about 64 to 155% over the amount originally Table IV below. of ammoniated and unammoniated sugar-con- Table IV NHg'AddGd Time Free NH; "Fixed" N Total N Expt. (Per Cent of Heated Temp., H Brix (Per Cent (Per Cent (Per Cent No. Dry Solids), 1 O p on Sample), on Sample), on Sample), Per Cent Per Cent Per Cent Per Cent EXAMPLE V taining materials were used. Table V below gives Table II NH, Added Free NH, FixedN TotalN Expt. (Per Cent of Time, Temp., pH, Brk (Per Cent (Per Cent (Per Cent No. Dry Solids), hr. 0 on Sample), on Sample), onSample),

Per Cent Per Cent Per Cent Per Cent ControL. 74.2 35 3 7.5 75 8.1 68.5 0.53 1.75 2.19

EXAMPLE III was 3.60 and its nitrogen content 0.05. At the end of the heatin operation the pH was 9.45 and the nitrogen content 3.9 of which 0.8% was free NH3 and the fixed nitrogen in the final prod- In this set of experiments black strap cane molasses was ammoniated with anhydrous ammonia gas in the manner described in Example II. The results of the experiments are shown in Table III below. uct 3.1%.

Table III M 1 gm xm e Time T (g ue/ Nils (1;FlxedtN (pToal 1;:

o asses er en 0 emp; er en on er en on er en on Expt Taken; g. Dry Solids) jg f0. P Bdx Sample), Per Sample), Per Sam le), Per

- Per Cent Cent Cent ent 5.1 85.8 0.39 5.1 86.0 0. 55 800 2. 0 8 75-85 3 80. 2 0. 6O 1. 59 2. 09 800- 2. 0 5 75-80 8- 4 80. 2 0. 86 1. 7B 2. 47 800 4- 0 8 75-80 9. 2 77. 5 1. 64 2. 09 3. 44 500 4. 0 24 75 8. 1 76. 2 0. 95 2. 44 3. 22 400 4. 1 21 75 8. 6 78. 1 1. 03 2. 37 3. 22 800 I 4. 1 24 75 9. 4 76. 7 l. 76 2. 21 3. 66 400 7. 0 4 75-30 9. 9 74. 0 3. 24 1. 93 4. 59 400 7. 0 8 75 9. 9 75. 5 2. 46 2. 33 4. 35 800 7- 0 8 75 10. 2 72. 7 3. 61 2. 14 5. 11 400 7. 0 l1. 5 75 9. 7 75. 7 2. 57 2. 03 4. 15 750 7. 0 24 75 9. 6 72. 8 2. 69 2. 46 4. 67 500 7. 7 7 75 9. 6 75- 7 2. 98 1. 98 4. 44 400 14. O 4 75-80 9. 6 77. 9 2. 06 2. 06 3. 76 400 I 15. 4 12 9. 8 75. 3 2. l8 2. 01 I 3. 81

1 Sealed reactor.

EXAMPLE IV EXAMPLE VI Blackstrap cane molasses was treated at a Brix of 75 with unpurified, autolyzed yeast at about 60 C. for seven hours. The amount of invert sugar was thus increased by an amount ranging Molasses distillation syrup (CDMS), ammoniated as described in Example II above, gave a product having a protein equivalent of 12.5%.

Feeding tests conducted with the ammoniated sugar-containing syrup described above have shown the materials to be eminently satisfactory sources of proteins for animal feed and particularly forruminants and also to be of satisfactory palatabllity. In these tests various mixtures present.

Inverted cane molasses prepared asabove de-- scribed or by inverting with the enzyme invertase was. subjected to ammoniation as described in Example II. The results of the ammoniatlon of 500 gram lots of inverted molasses are shown" in Anhydrous ammonia gas was passed through a .75 the composition, of the various ammoniated s'ugar oontainingmateri' ls used in the feeding .llhe; :feed; rations; described in Table.- VI; above tests-reported below; were fed. to; 12. to; 14 week. old bull calves." Dim Table: V 1

r SaltPresent Protein Equiv. Add Used No. Material gum -73p fi mounl a a a on.- erceu Sample) Kind on I Sample Ammoniated inverted blackstrap molasses- 26. 2. none l6 Ammoniated inverted blackstrap mo- 11. 2 none lasses, Untreated blackstrap molasses. O fln 13.8 sPO4 0.9.- D dO 13. 8 E1504..." 1. 2 E Ammonjated inverted blaekstrap molasses. 27. 5 H01 NH 2. 8 F... do 30;0' H580 5. 2 G Ammoniatedblackstranmolasses. 16: 8 H01 9;

15.0 H280 1.1 I... 2----(10. 1.5: 6 113204.--- 1.2 J Ammoniated inverted blackstrap molasses 29'. 4 HBPQL 1J5;

Ammoniated blackstrap molasses '15. 0 none.

$4 Ammoniated inverted blackstrap mo- 13. 8 HO] 0. a I lasses, Untreated blaclrstrap molasses. I

Ammoniated hydrol syrup 26. 8 H POi- Ammoniated molasses distillation syrup 1?.

1 Calculated from amount of acid used for neutralization of free ammonia.

The above samples of ammoniated. sugar-eontaining syrups were used in preparing the feed rations shown in Table VI below.

ing the preliminary period of observation each received fivepounds. of the Control mix (Table VI) for. seven days and six pounds of the same mix Table VI .RA-TIONS Ingredient if; A B 0- D E' 1 F G. H I .T' K L M N Molasses I (Cane) 20 17.06 4.46 8.66 8.66 1.7256 18. 26' 121.86v 10. 06 10.66 18.06 13. 76 8.66 17. 3 6. 8 Molasses 11 (Am. Molasses) ,9.4 22 17.8, 17.8 8.9. 8.2. 14.6 16.4 15.8 8.4 12.7 17.8 9.2 19. 7 30 1bs. Soybean oil meal 10 3. 54 3. 54 3. 54 3. 54 3. 54 3. 54 3. 54 3. 54 3. 54 3. 54 3. 54 3. 54 3. 54 3. 54 Wheat bran '20 20 20 20 20 20 20 20 20' 20' 20 20 2O 20 20 Crushed oats. 60 60 6O 60 60 60 60 60 6O 60 60 60 60 60 Cracked corn 84 84 84 84 84 84 84 84 84 84 84 84 84 84 84 Irradiated yeast (9F) .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 .2 I .2 .2 .2 170.2 lbs. Salt 2 '2 2 2 2 2 2 2 2 2 2 2 "2 2 2 ,Dioaloium Phosphat 2 2 2 2 2' 2 2 2 2 2 .2 .2 -2 2 2 Bone Meal q; 2 2 2 2' 2 2 2 a 2 2 2- 2 2 -2 v 2 2 The above rations were usedin first trial. The-control ration was altered-bvchanges in the molasses and soybean oil meal contents only 'llhetotal protein of-the lowest concentration molasses (B) wasusedas abuse '(22X11;2%" Protein= 2146 lbs. of protein). of protein trom each sample of molasses a total of3.54 lbs. of soybean oil mea1:(38% .Dig. Protein) was used asasbase.

O11 the basis of 2.46'lbs for the-:next, seven days-covering a total-14 jday stabilization period. They were also. fed. extra .leafy seoondi cutting alfalfa hayad libitumduringtl'iis'period. 2

During the experimental period thecon-trol and experimental. groups all received six pounds of concentrateieed (Table VI) per day for 15 days. "Ihey were; limited to threepounds: oiwthe same hay per day during, this; period. The proteineon- V RationA. H

I 7 Dig. 1 7 Protein Cane Molasses 17. 06 Ammoniated Mol1asses 9. 4 2. 46 Soybean Oil meal i 3. 54 1.35

Total ..,I.,.. 18.81;

Ration? Lbs. 1 Protein Cane Molasses 4. 46 Ammoniated Molasses 22 2. 46 Soybean Oil Meal 3. 54.. 1.35

' Total"... 3.

lbs. Diapmteininldlhs. oisoy- I tent of the feed mixtures was low and the total intake limited during the experimental period; This'was: done purposely-so as to provide as severea testas possible in order to define-diff- I ferences. between samples of the ammoniated sugar-containing materials. The. growth dataare presented in Tables VII and VIII below. Except as specifically noted, the results shown represent the averages obtained from two calves fed the same rations. Y

[Final data I on 15 day feeding trial. (Ammoniated product) Basal Period (14 Da.) I 3W PQ P Group P Beginning G err Daily u l Daily am Cent Gain Cent x eight Gain a Gain 00111101.. 202 23 11. 4 1. 64 23 1.0. 2 1. 53 A 204 26 12. 7 1. 86 23 10. 1. 53 B 205. 20. 5 9. 9 1. 46 27. 8 12. 4 1. 85 C 204 22. 5 1.1. O 1. 61 20. 5 9. 0 1.. 37 D 181 19. U 10. 5 1. 36 24. 5 12. 3 1. 63 E 204. 5 23. O 11. 2 1. 64 19. 5 8. 6 1. 30 F 197. 5 25. 0 12. 7 1. 79 27. 0 12. 1. 1. 80 G 194 26. 5 13. 7 1. 89 25. 0 11. 3 1. 67 H 194. 5 22. 5 10. 4 1. 61 21. 3 9. 8 1. 42 L 191. 5 25. 0 13. 0 0. 9D 19. 5 9. 0 1. 30 1.. 213. 5 34. 0 15. 9 2. 4O 32. O 12. 9 2. 13 K. 196 24. 5 12. 5 1. 75 20. 5 9. 3 1. 37 L 197 21 10. 7 1. 50 21. 0 9. 6 1. 40 M. 204 31. 5 15. 4 2. 25 34. 5 14. 6 2. 30 N 209. 5 24. 0 11. 5 1. 71 3G. 5 15. 6 2. 43

1 Data on only 1 calf, other suffered from pneumonia and not included.

Basal period-preliminary period of observation and stabilization.

Experimental period-Calves on ammoniated molasses with an equivalent amount of protein from each sample of molasses.

1 All data expressed in lbs. except where designated as per cents.

Table VIII HEIGHT AT THE WITHE RS [Final date 1 on day feeding trial. (Ammoniated product) Basal Period (14 D Experimental Period Group F Per Beginning Gain g Daily G Daily aln Cent Height Gain Gain Gain Gain 1 Data on only 1 calf, other sufiered pneumonia and not included.

Basal periodpreliminary period of observation and stabilization.

Experimental period-calves on ammoniated molasses with an equivalent amount of protein from each sample of molasses.

2 All data expressed in cm. except where designated as per cents.

The results of the above feeding tests show conclusively the eflicacy of my new ammoniated sugar-containing product as a. constituent of mixed feed for ruminants. It can also be used satisfactorily as an ingredient of other feedstuffs, the proportions of the materials usedbeing regulated in accordance with the desired protein content of the finished feed and the availability of other nitrogen-containing materials for use in formulating the finished feed.

EXAMPLE VII Continuous ammoniation of blackstrap molasses was efiected by pumping a. reaction mixture consisting of 0.6 lb. NH; and 9.35 lbs. blackstrap molasses at the rate of 9.35 lbs. of reaction mixture per hour and at a pressure of 60 pounds per square inch through 142 feet of A; inch pipe in the form of a coil and heated to 130 C. The residence time of the reaction mixture in the resatisfactory ammoniation inthis type'reactor at pressures ranging, from} .50. to 500;;pounds. per; square-inch: with residence times ranging from 4' to; .64; minutes-and reaction temperatureupto.

Continuous ammoni'ati'on of citrusm'ola'sses was efiected by pumping a reaction mixture consisting of 13.5 lbs. NHs and 538 lbs. citrus molasses at the rate of 30.3 lbs. of reaction mixture per hour and at a pressure of 125 pounds per square inch through 180 feet of A; inch standard pipe in the form of a. coil and heated to 120 C. The residence time of the reaction mixture in the reactor Was 13.7 minutes. The product from the reactor contained'3.12% total N and 0.81% free NHs.

Now having described my invention, what I claim is: g V

1. A method of converting ammonia into a nitrogen form readily assimilable by ruminants which comprises subjecting ammonia to reaction with a sugar-containing material selected from the group consisting of blackstrap molasses, inverted blackstrap molasses, hydrol syrup, wood sugar syrup, citrus molasses, and condensed distillers molasses solubles.

2. The process of claim 1 in which the reaction is carried out at temperatures ranging from 20 to 150 C.

3. The process of claimv 1 in which the said reaction mixture is heated at temperatures ranging from 80 to 140 C. fora period of time ranging from /2 to hours.

4. A 'method of converting ammonia into a nitrogen form readily assimilable by'ruminants which comprises reacting a sugar-containing material selected from the group consisting of blackstrap molasses, inverted blackstrap molasses, hydrol syrup, wood sugar syrup, citrus molasses and condensed distillers molasses solubles with an amount of ammonia sufiicient to give a reaction product having a pH less than about 9.5 when substantially all of the ammonia is reacted with the sugar-containing material.

5. A method of converting ammonia into a nitrogen form readily assimilable by ruminants which comprises reacting a sugar-containing material selected from the group consisting of blackstrap molasses, inverted blackstrap molasses, hydrol syrup, wood sugar syrup, citrus 'molasses, and condensed distillers molasses solucomprises adding ammonia to molasses and then 9.5 and containing nitrogen in a form utilizafile' oY-wuminants.

:9;-'21- mtrogen-'ontaining feedasupplementimt -5 mmifimwhioh comprises'iihezi eadtiompzodlwt f ammonia with a, sugarwontaining material seleeted from flre group consistmg' ofablackstmp molasses, inverted blackstrap molasses, liydrdl syrup, wood sugar'syrup, molasses, and condensed distillers molasses solubles, said reaction 4sproduct hawing --a. pH manging item "1.5 qto 12 9.5 and a protein eqiifvalehfi of from 12.5 to 36 per cent.

.HUGH R. STJLES.

"REEERENOES CITED The following references are of "record in the file of this pa;tent:

UNITED STATES PATENTS Name Date 

1. A METHOD OF CONVERTING AMMONIA INTO A NITROGEN GORM READILY ASSIMILABLE BY RUMINANTS WHICH COMPRISES SUBJECTING AMMONIA TO REACTION WITH A SUGAR-CONTAINING MATERIAL SELECTED FROM THE GROUP CONSISTING OF BLACKSTRAP MOLASSES, INVERTED BLACKSTRAP MOLASSES, HYDROL SYRUP, WOOD SUGAR SYRUP, CITRUS MOLASSES, AND CONDENSED DISTILLERS MOLASSES SOLUBLES. 